N-halosulfoximines

ABSTRACT

SULFOXIMINES HAVING A LONG CHAIN ALKYL GROUP, A SHORT CHAIN ALKYL GROUP AND AN ACTIVE HALOGEN ARE USEFUL AS ANTIBACTERIAL, ANTIFUNGAL AND BLEACH COMPOUNDS, PARTICULARLY IN COMBINATION WITH AN ALKALINE BUILDER SALT.

XR 3557206 EX United States Patent Oflicc Patented Jan. 19, 1971ABSTRACT OF THE DISCLOSURE Sulfoximines having a long chain alkyl group,a short chain alkyl group and an active halogen are useful asantibacterial, antifungal and bleach compounds, particularly incombination with an alkaline builder salt.

BACKGROUND OF THE INVENTION OBJECTS It is an object of this invention toprovide an organic compound containing a nitrogen-halogen group which isan effective antibacterial, antifungal and bleaching material and which,when hydrolyzed, can also provide surface activity and detergency to anaqueous medium.

SUMMARY OF THE INVENTION The class of compound of thisinventioncomprises N- halosulfoximines of the following formula:

R is methyl or ethyl and X is Cl, Br or I. The C -C alkyl, methyl,chloro or bromo compounds are preferred. The compounds of the inventionare preferably used with an alkaline salt which provides a pH in aqueoussolution of from about 8 to about 12.

DETAILED DESCRIPTION Unsymmetrical dialkyl sulfoximines having detergentproperties are known and described in U.S. Pat. 3,255,116 issued to JimS. Berry on June 7, 1966. The corresponding N-halosulfoximines can beprepared by halogenating the Berry sulfoximines with a hypochloritecompound, such as NaOCl, NaOBr or NaOI or with elemental halogen such asCl,, Br, or 1,. Either method of halogenation is under conditions whichare conventional for the halogenation of organiocompounds containing anNH grouping. Such conventional halogenating conditions preferablyinvolve aqueous solution, temperatures ranging from 0' C. to 50 C., a pHin the range of 10 to 13, agitation, and a quantity of halogen rangingfrom 1.0 to

'5 moles per mole of the compound containing the NH of halogenation of8,5 dimethyl sulfoximine is found in an article by Rolf Appel et al.-,in Chemische Berichte, Jahrg. 99, pages 3108-3117 (1966) entitled Uberdie Chloraminierung von Thiriithern. s

group. An example Specific examples of the compounds of this inventioninclude the following:

decyl methyl N-chlorosulfoximine, dodecyl methyl N-chlorosulfoximine,dodecyl methyl N-bromosulfoximine, dodecyl methyl N-iodosulfoximine,tetradecyl methyl N-chlorosulfoxirnine, tetradecyl ethylN-iodosulfoximine, hexadecyl ethyl N-chlorosulfoximine, dodecyl ethylN-bromosulfoximine.

The N-halosulfoximines of this invention hydrolyze in aqueous solutionto form active halogen which functions for antibacterial, antifungal orbleaching purposes, leaving the sulfoximine molecule as a surface activeagent and detergent to facilitate the action of the active halogen aswell as providing detergency to the solution being employed for thesepurposes. Most desirable results are achieved when the N-halosulfoximineis used with a water-soluble alkaline compound which provides a pH inaqueous solutions in the range of about 8 to about 12, preferably in aweight ratio of N-halosulfoximine to alkaline compound ranging fromabout 5:1 to about 1:20.

The alkaline compounds used with the N-halosulfoximines include bothwater-soluble inorganic and organic alkaline salts, preferably thosesalts which act as builder salts. Such builder salts function with thesulfoximine detergent resulting from hydrolysis of the N-halo compoundto enhance the detergency characteristics thereof.

Examples of suitable water-soluble, inorganic alkaline detergencybuilder salts are alkali metal carbonates, borates, phosphates,polyphosphates, bicarbonates, silicates and sulfates. Specific examplesof such salts are sodium and potassium tetraborates, perborates,bicarbonates, carbonates, tripolyphosphates, pyrophosphates,orthophosphates and hexametaphosphates.

Examples of suitable organic alkaline detergency builder salts are: (1)Water-soluble aminopolyacetates,

e.g., sodium and potassium ethylenediaminetetraacetates,-

nitrilotriacetates and N-(2-hydroxyethyl)-nitrilo diacetates; (2)Water-soluble salts of phytic acid, e.g., sodium and potassiumphytates-see U.S. Pat. 2,739,942; (3) Water-soluble polyphosphonates,including specifically, sodium, potassium and lithium salts ofethane-l-hydroxy- 1,1-diphosphonic acid, sodium, potassium and lithiumsalts of methylene diphosphonic acid, sodium, potassium and lithiumsalts of ethylene diphosphonic acid, and sodium, potassium and lithiumsalts of ethane-1, 1,2-triphosphonic acid. Other examples include thesealkali metal salts of ethane-2-carboxy-l,l-diphosphonic acid,hydroxy-methanediphosphonic acid, carbonyldiphosphonic acid,ethane-l-hydroxy-1,1,2-triphosphonic acid, ethane-2-hydroxy-1,1,2-triphosphonic acid, propane-1,l,3,3-tetraphosphonic acid,propane-1,1,2,3-tetraphosphonic acid, andpropane-1,2,2,3-tetraphosphonic acid; (4) Watersoluble salts ofpolycarboxylate polymers and copolymers as described in the patent ofFrancis L. Diehl, U.S. 3,308 067 issued Mar. 7, 1967. Specifically, adetergent builder material comprising a water-soluble salt of apolymeric aliphatic polycarboxylic acid having the following structuralrelationships as to the position of the carboxylate groups andpossessing the following prescribed physical characteristics: (a) aminimum molecular weight of about 350 calculated as to the acid form;(b) an equivalent weight of about 50 to about calculated as to acidform; (c) at least 45 mole percent of the monomeric species having atleast two carboxyl radicals separated from each other by not more thantwo carbon atoms, (d) the site of attachment to the polymer chain of anyearboxy-containing radical being separated by not more than three carbonatoms along the polymer chain from the site of attachment of the nextcarbonyl-containing radical. Specific examples are polymers of itaconicacid, aconitic acid, maleic acid, mesaconic acid, fumaric acid,methylene malonic acid, and citraconic acid and copolymers withthemselves and other compatible monomers such as ethylene.

Mixtures of organic and/or inorganic builders can be used and aregenerally desirable. One suc ture of builders is disclosed in CanadianPat Burton H. Gedge, e.g., ternary mixtures o 'polyphosphate, trisodiumnitrilotriacetate and trisodium ethane-1- hydroxy-1,l-diphosphonate. Theabove described builders can also be utilized singly in this invention.

The preferred builder salts are sodium tripolyphospha and sodiumnitrilotriacetate, alone or in admixture.

The compositions of this invention can contain, if deaired, in additionto the N-halosulfoximine and alkaline salt, any of the usual additiveswhich make them more attractive or effective. For example, perfumes,dyes, proteolytic enzymes, corrosion inhibitors, other chlorinebleaches, soil antiredeposition agents and optical brighteners can beused. The compositions can also contain other organic detergents of thefollowing classes: watersoluble fatty acid soaps; anionic syntheticnon-soap detergents; nonionic synthetic detergents of the ethoxylate orsemipolar type; zwitterionic synthetic detergents; ampholytic syntheticdetergents.

The compounds and compositions of this invention are described in thefollowing examples which are illustrative thereof but are not limiting.

EXAMPLE I Preparation of decyl methyl N-chlorosulfoximine Decyl methylsulfoximine (4.0 g. or 0.0182 mole), M.P. 50-52" C. was suspended inabout 40 ml. water and to it was added, with vigorous shaking, 50 ml.5.25% aqueous sodium hypochlorite (Clorox). After about three minutesshaking at 25 C., the insoluble product was harvested by filtration,air-dried, and recrystallized from hexane to give a white productmelting at 50-51 C.

For analytical purposes the product when mixed with the startingsulfoximine gave a mixed melting point depression to 35-37 C.Furthermore, while the infrared spectrum of the product was generallysimilar to the starting sulfoximine, the sharp, fairly intense NHstretching absorption'at 3.05;. seen in the sulfoximine was missing inthe N-chloro derivative. Analyses on the product gave percent N=5.4(calc., 5.5); percent S=13.1 (calc., 12.6); and percent Cl=l3.4 (calc.,14.0).

EXAMPLE II Preparation of decyl methyl N-bromosulfoximine A solution ofaqueous sodium hypobromite was prepared by chilling 200 ml. of 1.0 Naqueous sodium hydroxide to 0.5 C. and adding 16.0 g. (0.1 mole) brominedropwise with stirring. The cold solution was stirred until homogeneous.To a suspension of 4.0 g. of decyl methyl sulfoximine in 40 ml. waterwas added 75 ml. of the cold, aqueous sodium hypobromite solutionprepared above. After three minutes vigorous shaking, the product washarvested by filtration, air-dried, and recrystallized from hexane.

The yellow-colored product melted at 48-50 C.; a mixed melting pointwith the starting sulfoximine was depressed to 37-39 C. Infrared spectraof the product showed no NH stretching absorption at 3.05;characteristic of the starting sulfoximine.

r The procedure of Example I was used to prepare tetradecyl methylN-chlorosulfoximine by using tetradecyl methyl sulfoximine instead ofthe decyl compound. Decyl methyl N-iodosulfoximine was made by theprocedure of Example II by substituting iodine for bromine.

4 EXAMPLE III I Preparation of dodecyl methyl N-bromosul foximineDodecyl methyl sulfoximine in 1,2-dimethoxyethane (monoglyme) solventwas reacted with a molar equivalent of sodiumiiydride (stirredthree-neck flask protected from air with nitrogen) to form dodecylmethyl N-sodiosulfoximine. One molar equivalent of bromine was addedslowly, with stirring, to the solution. Removal of the precipitatedsodium bromide by filtration gave a solution in unonoglyme of dodecylmethyl N-bromosulfoximine.

EXAMPLE IV Bactericidial evaluation of tetradecylmethyl N-chlorosulf"oximine was made by the following procedure Test solutions: Cidal testswere carried out in FDA broth.

Organisms: One ml. of a 24-hour culture of Staphylococcus aureus andEscherichia coli containing approximately 250 x 106 organisms per ml.was used as the inoculum.

Media: FDA broth (5 g. Bacto Beef Extract, 10 g. Bacto Pcptone, 5G C.P.grade NaCl in 1,000 ml. distilled water). Difco Nutrient Agar wasemployed. Procedure:

(a) To tubes containing the tetradecyl methyl N- chlorosulfoximine at aconcentration of p.p.m. in FDA broth was added 1 ml. of a 24-hourculture of the organism and these were shaken thoroughly and placed in awater 'bath at 37 C.

(b) A 1 ml. transfer from a tube indicated in (a) was made after 10minutes of contact of the organism with the N-halosulfoximine into 100ml. of 5% sterile horse serum in distilled water. Additional dilutionswere made from the horse serum so that the number of colonies per platefell in a countable range. Dilutions also served to counteract possiblestatic etfects of the additive carried over in the original transfer.The dilutions were plated in nutrient agar.

(c) After 48 hours of incubation at 37 C., plates gere counted and theresults expressed as percent il.

(d) Controls were run in the matrix as well as in distilled water.

At 100 p.p.m., methyl tetradecyl N-chlorosulfoximine gave 99.9% kill ofS. aureus and 99% kill of E. coli.

EXAMPLE V Determination of fungicidal and fungistatic activity of decylmethyl N-halosulfoximines A spore suspension (1.0 ml.) of Microsporumgypseum was used to inoculate petri plates containing from 15 to 20 ml.of Sabourauds Detrose Broth (Difco) and the plates were subsequentlyincubated at 25 C. for two weeks. This period of incubation allowed theorganism to grow over the entire surface of the broth, thus forming atough mycelial mat. This mycelial mat was then cut by means of a sterilecork borer (12 mm. diameter) into mycelial plugs."

Fungicidal activity was determined by immersing the plugs into 100 ml.of a solution of the N-halosulfoximine compounds for various lengths oftime. The mycelium was kept submerged by agitating the solution with amagnetic stirrer. At 0, 5, 10, 20, 30 and 60 minutes after initiation ofthe test, mycelial plugs were removed and given two rinses, each ofapproximately five minutes duration, in 100 ml. of sterile distilledwater. The washed mycelial plugs were plated onto Sabourauds DextroseAgar (Difco) and observed periodically for growth. If no growth was0bserved from a given mycelial plug after seven days of incubation at 25C., the organism was considered to have been killed by the experimentalmaterial in the time interval indicated. Fungicidal activities weremeasured using this procedure with decyl methyl N-chloroandN-bromosulfoximines. Both compounds killed the organism, M. Gypseum,upon exposures between 30 and 60 minutes.

Fungistatic activity was determined by the agar incorporation method.The experimental material was incorporated into Sabourauds Dextrose Agarat 100 and 1,000 p.p.m. after the agar had been sterilized and cooled to45 C. The agar was then poured into plates and inoculated with myeelialplugs" (described above) and incubated for 14 days at 25 C. At that timethe concentration required to prevent growth of the fungus wasascertained. Both decyl methyl N-chloro and N-bromosulfoximinesexhibited fungistatic activity at 1,000 p.p.m.

COMPOSITION EXAMPLES Alkaline compositions having the followingformulations and pI-ls ranging from 8 to 12 can be prepared with theN-halosulfoximines of this invention incorporated therein. In solutionthe N-halosulfoximines hydrolyze to provide active chlorine anddetergency. The compositions impart eflective antibacterial andantifungal action on fabrics cleansed in solutions of the composition aswell as cleansing and bleaching the fabrics.

A water solution containing 0.15%, 0.3% and 0.45%

I concentrations of the above formula provides antibacterial, antifungaland stain removal results in household laundering of fabrics.

EXAMPLE vni The following granular laundry composition containing aneffective chlorine bleaching agent performs very well in cleaning,whitening and antibacterial activity.

Percent Tetradecyl methyl N-chlorosulfoximine 7 Sodium lineardodecyl-benzenesulfonate 17 Sodium tripolyphosphate 50 Sodium carbon 10Sodium sulfate--- 10 Moisture Balance I, 6 EXAMPLE IX Another chlorinebleach composition according to this invention suitable for bleachingstained cotton fabrics has the following composition:

\Percent Decyl methyl N-chlorosulfoximine 20 Trisodiumethane-1-hydroxy-l,l-diphosphonate ..40 Trisodium nitrilotriacetateuu L40 EXAMPLE X An antibacterial laundry detergent has the followingformula:

The foregoing description of the invention has been presented describingcertain operable and preferred embodiments. It is not intended that theinvention should be limited since variations and modifications thereofwill be obvious to those skilled in the art, all of which are within thespirit and scope of this invention:

What is claimed is:

1. N-halosulfoximine of the following formula:

wherein R is an alkyl group containing 10 to 16 carbon atoms, R ismethyl or ethyl and X is Cl, Br or I.

2. The sulfoximine of claim 1 wherein R is decyl, dodecyl or tetradecyl,R is methyl and X is Cl or Br.

3. The sulfoximine of claim 2 wherein X is Cl.

References Cited UNITED STATES PATENTS 3,255,116 6/1966 Berry 260551HENRY R. JILES, Primary Examiner HARRY I. MOATZ, Assistant Examiner US.Cl. X.R. 25299

